Polymeric halogenated organophosphorus diols

ABSTRACT

Polymeric halogenated organophosphorus diols are obtained by reacting chlorine or bromine with spirocyclic phosphites and thereafter reacting the halogenated product with a diol, in the presence of an acid acceptor. These novel viscous polymers react with polyisocyantes to produce polyurethanes. Polyurethanes so made are characterized by improved flame retardant properties compared with conventional polyurethanes. Such polyurethanes are preferably in the form of foams, especially flexible foams.

I United States Patent H 1 in] 3,882,199 Batorewicz 5] May 6, 1975 [5POLYMERIC HALOGENATED 3,423,486 l/l969 Ratz et al 6 260/928ORGANOPHOSPHORUS DIOLS 3,578,731 5/1971 Mange et al 260/973 X [75]Inventor: \CNadim Batorewicz, New Haven, Primary Examiner Lonaine A.weinbcrger Assistant Examiner-Richard L. Raymond [73] Assignee:Uniroyal, Inc., New York, NY. Attorney, Agent, or Firm-Robert 1.Patterson, Esq.

2 F] d: [1,1974 {2 1 Jan 57 ABSTRACT [2!] Appl. No.: 432,703 Polymerichalogenated organophosphorus diols are obtained by reacting chlorine orbromine with spirocy- 52 us. Cl 260/928; 260/25 AR; 260/973; Clicphosphites and thereafter reacting the haloge- 2 0 9g nated product witha diol, in the presence of an acid [51] Int. Cl. C07f 9/18 acceptor-These novel Viscous P y react with 58 Field of Search 260/928. 969, 973,986 Polyisocyanles to Produce polyurethanes- Polyurethanes so made arecharacterized by improved flame [56] R fere Cimd retardant propertiescompared with conventional UNITED STATES PATENTS polyurethanes. Suchpolyurethanes are preferably in 3,147,299 9/l964 Smith 8| al 260/928 xthe form of foam espec'auy foams 3,l92,242 6/1965 Birum 260/928 8Claims, N0 Drawings POLYMERIC HALOGENATED ORGANOPHOSPHORUS DIOLSBACKGROUND OF THE INVENTION The invention relates to polymerichalogenated organophosphorus diols. More particularly. the inventionrelates to processes for preparing these novel polymeric materials andutilizing the same along with other polyols. as co-reactants in theproduction of polyurethanes. Polyurethanes containing these novelpolymeric materials have superior flame retardant properties whencompared to conventional polyurethanes.

Organophosphorus compounds containing halogens are well known in theart. Many compositions of this broad class of materials have beenclaimed as flame retardants for a variety of polymers. includingpolyurethanes. A substantial portion of such materials are of theadditive type. That is. these materials are not chemically bound to thepolymer backbone. Such additive flame retardants are described. forexample. in the U.S. Pat. No. 3.192.242. The organophosphorus materialsdisclosed in this patent have the general fromula:

H X O wherein X is a halogen such as bromine or chlorine and Y is ahaloalkoxy group.

Reactive type flame retardants usually possess at least two reactivesites through which they are chemically bound to the polymer backbone.These retardants are superior to the additive type retardants, becausenot only will they not evaporate. sublime or leach out of the polymersubstrate during use or processing but they also form an integral partof the polymer structure.

Reactive type flame retardants such as chlorine containing phosphatepolyols have been employed to improve polyurethyane resins. Thesereactive flame retardants are typified in U.S. Pat. No. 3.423.486.

While various known reactive type flame retardants are useful in rigidtype polyurethane foam. they may not be employed advantageously in theproduction of flexible type foam. For example. the above mentionedphosphate polyols are tetrafunctional monomers. that is they possesslarge OH Numbers. and this characteristic makes them unsuitable ascorrectants in a flexible foam formulation which requires polyols havinga functionality in the range from 2 to 2.5. as well as an H number of100 or preferably less.

The polymeric halogenated organophosphorus diols of the invention areprepared by chlorinating or brominating a spirocyclic phosphite attemperatures from about -50C. to +50C. and condensing halogenatedreaction product with a diol in the presence of an acid acceptor. Thesenovel diols possess hydroxyl groups capable of forming urethane linkageswith isocyanates. Although the diols of the invention may be used alonewith polyisocyanates to form polyurethane-type poly- DESCRIPTION OF THEPREFERRED EMBODIMENTS Polymeric halogenated organophosphorus diols ofthe invention are represented by general formula I -CH,)O-D-OR' as I a xc wherein R may be:

a. hydrogen. chlorine or bromine; b. an alkyl. haloalkyl or alkoxyradical having from I to 6 carbon atoms; wherein u may vary from 1 to 3;wherein R may be:

c. a branched or linear alkylene. alkenylene. alkynylene oralkoxyalkylene radical containing from 2 to [0 carbon atoms; optionallycontaining bromine or chlorine substituents. wherein X may be chlorineor bromine; and wherein y typically has a value of from 1 to 5 but notmore than 7.

Those skilled in the art will appreciate that denotes an average valueand that particularly within polymers having a broad molecular weightdistribution species having v values somewhat greater than 5. e.g.. ashigh as 7. are possible. The diols of general formula I are preparedfrom spirocyclic compounds of general formula ll The above compounds maybe prepared according to U.S. Pat. No. 2.847.443.

While any of the spirocyclic phosphites containing aryl typesubstituents in the 3.9 position may be used. the preferred spirocyclicphosphites in the context of this invention are3.9-bis(phenoxy)-2.4.8.lO-tetraoxa- 3.9-diphosphaspiro [5.5] undecaneand 3.9-bis(pbromo-phenoxy )-2.4.8. I 0-tetraoxa-3 .9-diphosphaspiro[5.5] undecane.

Chlorine or bromine is added to the spirocyclic phosphate of structureII at atmospheric pressures to produce a halogen-containing Arbuzov typerearrangement product characterized by the phosphorohalidate ofstructure Ill.

wherein R. X and n have the meanings shown above. This reaction requiresexternal cooling during the step' wise addition of the halogen in orderto maintain temperatures preferably, from about -20 to +20C; however. Sto +50C. is operable. The intermediate phosphorohalidate issubstantially free of by-products and is conveniently prepared in situbefore the subsequent reaction with a diol.

The addition of the phosphorohalidate of structure lll to theappropriate diol in the presence of an acid acceptor such as a tertiaryamine produces the polymeric halogenated organophosphorus diols ofstructure I. This reaction is preferably carried out in the presence ofan acid acceptor such as a tertiary amine. for instance triethylamine.tripropylamine. pyridine. diethylaniline and others. in order to tie uphydrogen halide liberated during the reaction. by forming the respectiveamine hydrohalide salt.

The amine salt by-product of'the reaction is removed by filtration andthe filtrate is extracted with water to remove any residual amine salt.The organic phase is then concentrated under reduced pressure to removeany unreacted amines and diols. The polymeric halogenated phosphateester diol product remains as a pot residue.

A wide variety of inert organic solvents can be used advantageously inthis reaction. It is preferable. but not essential. to select a solventin which all reactants are soluble; especially the more insoluble diols.For example. benzene can be employed with triethylene glycol; chloroformwith l.2 propanediol or dipropylene glycol; and actonitrile withethylene glycol which is insoluble in the above-mentioned solvents.

Molar ratios of the diols per mole of the phosphite can vary from [.5 to2.0 moles of diol per mole of phosphite. The preferred ratio is 2:1.However. when a large excess of a diol is used. the unreacted portion ofthe diol may be removed by distillation. generally under reducedpressure.

A great variety of diols can be employed in the preparation of the novelcompositions of this invention. Preferred are diols including ethyleneglycol. diethylene glycol. triethylene glycol. 1.2- or 1.3 propyleneglycol. dipropylene glycol and tripropylene glycol. Other diols usefulfor the production of compounds of this invention include aliphaticdiols containing from 3 to about carbon atoms. These diols may be linearor branched and may bear either all primary or all secondary OH groupsor a mixture of primary and secondary OH groups. The polyols may alsocontain unsaturation or halogen substituents. Exemplary are diols suchas 2- butenediol-l.4. 2-butynediol-l.4. 2.3dibromo-L4- butanediol.2.3dichlorol .4-butanediol. 2.3-dibromolbutenediol-lA.3-bromo-l.2-propanediol. 3-chlorol.2-propanediol.2.2-bis(bromomethyl l.3- propanediol. and 2.2-bis( chloromethyl l .3-

propanediol. and the like. Higher molecular weight diols. such as.polyethylene ether glycols and polypropylene ether glycols may also beused in the invention.

There is no advantage in employing high functionality polyols such astriols. tetrols. hexols and the like be cause the products derived fromsuch polyols will possess high viscosity, functionality greater than twoand large OH Numbers. These properties will render the productsunsuitable as coreactants in a flexible urethane foam formulation wherelow viscosity, and functionality between 2 and 2.5 as well as OH Numbersof l00 or less are sought.

The polymeric halogenated organophosphorus diols according to theinvention are oily materials which are neutral to moist litmus. Thesepolymers are soluble in polyether polyols normally employed inpolyurethane production as well as most common organic solvents. Goodsolubility renders the polymers of this invention especially useful inpolyurethane foams where homogeneity and low viscosity of the polyolcomponents are important.

The invention will now be described by reference to specific examples;however. in no way should these specific examples be interpreted aslimiting the scope of the present invention.

EXAMPLE 1 Chlorine gas is passed through a solution of 3.9-bis(phenoxy)-2.4.8.l0-tetraoxa-3.9-diphosphaspiro [5.5] undecane (l50g.. 0.42 moles) in benzene (500 ml.). for a period of 5 hours. Duringthe addition the temperature of the solution is kept below 25C by meansof an ice-water bath. Following addition. the pale yellow coloredsolution is concentrated to about one-half volume under aspiratorpressure and then added dropwise with stirring to a benzene solution(800 ml.) of triethylene glycol (lSO g.. L20 moles) and triethylamine(83.0 g.. 0.79 moles); thereby causing a slow temperature rise to about50 to 60C. The resulting mixture is refluxed for 4 hours and keptovernight. Thereafter the amine salt is separated by filtration and thefiltrate is first concentrated under an aspirator pressure and thenunder about 0.3 mm pressure of Hg at to [35C pot temperature to removethe excess glycol. The resulting polymeric diol is a brown oil. which isneutral to moist litmus.

Anaiysis: OH Number 108; 8.437(1 9.1 l7rCl; y =19 (average) EXAMPLE 2 Asolution of bromine (85.0 g, 0.53 mole) in chloroform (lOO ml.) is addeddropwise with stirring to a solution of3.9-bis(phenoxy)-2.4,8.l0-tetraoxa-3.9- diphosphaspiro [5.5] undecane[00 g.. 0.26 moles) in chloroform (200 ml. During the addition thetemperature of the reaction solution is kept at about 5 to [0C. by meansof an ice-water bath. Upon completion of the addition reaction thesolution acquired a permanent brownish color.

This brownish colored solution is added dropwise with stirring to asolution of ethylene glycol (76.0 g.. 1.23 moles) and triethylamine H28g.. L22 moles) in acetonitrile (400 ml. thereby causing a slowtemperature rise. The resulting solution is kept under reflux for l hourand then concentrated under an aspirator pressure.

The residue is diluted with chloroform (800 ml.) and then washed withtwo 300 ml. portions of water prior to drying over anhydrous sodiumsulfate.

The chloroform solution is then concentrated under an aspirator pressureand finally under about 0.5 mm pressure of Hg at 50 to 70C pottemperature. The polymeric diol obtained is a dark tan oil which isneutral to moist litmus.

Analysis: OH Number 67; 7.62P; 25.8792 Er; y 2.7 (average) EXAMPLE 3 Asolution of 3,9-bis(phenoxy)-2.4,8.lO-tetraoxa- 3.9-diphosphaspiro [5.5]undecane 100 g.. 0.26 mole) in chloroform (200 ml) is treated withbromine as in Example 2. The resulting brownish solution is addeddropwise with stirring to a solution of triethylene glycol (239 g.. 1.59moles) and triethylamine (lll g.. [06 moles) in chloroform (400 ml.);thereby causing a slow temperature rise to 40C. The resulting solutionis kept under reflux for 3 hours and then allowed to stand overnight.Then, the reaction solution is diluted with chloroform (300 ml.); washedwith diluted hydrochloric acid; washed with sodium carbonate solution;and finally washed with water. The chloroform phase is dried overanhydrous sodium sulfate and then concentrated under aspirator pressureand then under about 0.5 mm pressure ofHg at 50 to 70C. pot temperature.

The polymeric diol obtained is a light tan oil.

Analysis: OH Number 89; 7.977rP; [9867: Br; y 1.6 (average) EXAMPLE4 Asolution of 3.9bis(p-bromophenoxy)-2,4.8,l-

tetraoxa-3.9-diphosphaspirol5.5] undecane (114.0 g.,

0.21 mole) in chloroform (250 ml.) is treated with bromine as in Example2. The resulting colored solution is added dropwise with stirring to asolution of 1,2- propanediol (32.0 g., 0.42 mole) and triethylamine(43.0 g.. 0.42 mole) in chloroform (300 ml.); thereby causing a mildexotherm.

The resulting solution is refluxed for 2 hours; washed with two 250 ml.portions of water; and dried over anhydrous sodium sulfate. Then. thesolution is concentrated. first under aspirator pressure and finallyunder about 0.1 mm. pressure of Hg at about 100C. pot temperature.

The polymeric diol obtained is a viscous tan oil (131.0 g.) which isneutral to moist litmus.

Analysis: OH number 44; 7.02'71P; 40.42% Br. y 4(average) EXAMPLE 5 Asolution of 3,9-bis(phenoxy)-2.4.8.l0-tetraoxa- 3.9-diphosphaspiro [5.5]undecane (280.0 g., 0.74 mole) in chloroform (600 ml.) is treated withbromine as in Example 2. The resulting brownish solution is con-Centrated under an aspirator pressure to about 450 ml. and addeddropwise with stirring to a solution of dipropylene glycol (2000 g..1.48 moles) and triethylamine (152.0 g. 1.5l moles) in chloroform (800ml); thereby causing a gradual rise in temperature to about 55C.

The resulting solution is refluxed for 2 hours; washed with two 250ml.portions of water and dried over anhydrous sodium sulfate. Then, thesolution is first concentrated under an aspirator pressure and finallyunder about 0.1 to 0.3 mm. pressure of Hg at about 100C pot temperature.

The polymeric diol produced (498 g.) is a tan oil which is neutral tomoist litmus.

Analysis: OH Number 58; 8.757cP; 20.397cBr; y =2.6( average) it will beobvious that in the products made according to the foregoing specificexamples the group R has the structure indicated below:

This example illustrates the utility of the polymeric polyolcompositions in the production of flameretardant polyurethane foams.

Stannous octoate (0.3 g.; M&T, T-9 (trademark an amine type catalyst (03g; Houdry. Dabco 33-LV (trademarkJ). a silicone surfactant (4.0 g.;Union Carbide. L-520 (trademark)). and water (6.4 g.) are combined witha solution of a polyether polyol having an OH number of 48.5 and amolecular weight of about 3500 (158 g.; Union Carbide. 1446 Polyol(trademark)), and the phosphate ester diol having an OH Number of 58.1(42 g.; prepared as in Example 5).

The above ingredients are thoroughly mixed and combined with toluenediisocyanate (76.2 g.. an :20 mixture of 2,4-and 2.6-isomers). Theresulting foam is subjected to a 10 minute post cure cycle at C. A foamhaving fine open cells and excellent resilience is obtained.

The foam thus produced is rated as self-extinguishing utilizing the ASTMD-1692 flammability test.

A comparison foam prepared as described above but using the conventionalpolyether polyol instead of the polymeric diol of Example 5 was testedand rated as burning by the same test.

What is claimed is:

l. A polymeric halogenated organophosphorus ester diol having thestructure 0 CH X n 2 HOR' C-P-OCPi- 43H O-P-OQ' OH I l 2 I O CH X T y na.

wherein R may be;

217 hydrogen. chlorine, or bromine.

b. an alkyl, haloalkyl or alkoxy radical having from l to 6 carbonatoms;

wherein it may vary from 1 to 3; wherein R may be:

c. a branched or linear alkylene, alkenylene. alkynylene oralkoxyalkylene radical containing from 2 to l carbon atoms; optionallycontaining bromine or chlorine substituents.

wherein X may be chlorine or bromine; and wherein y has a value of from1 to 7.

2. A polymeric halogenated organophosphorus ester diol as set forth inclaim 1 wherein R is hydrogen; and R' is CH CH OCH CH 0-CH CH 3. Apolymeric halogenated organophosphorus ester diol as set forth in claim2 wherein X is chlorine.

4. A polymeric halogenated organophosphorus ester diol as set forth inclaim 2 wherein X is bromine.

S. A polymeric halogenated organophosphorus ester diol as set forth inclaim 1 where R is hydrogen; and R is CH. ,CH,-.

6. A polymeric halogenated organophosphorus ester diol as set forth inclaim 5 wherein X is bromine groups are p-bromophenyl; X is bromine; and

8. A polymeric halogenated organophosphorus ester diol as set forth inclaim I wherein R is hydrogen; and

CH CH

1. A POLYMERIC HALOGENATED ORGANOPHOSPHORUS ESTER DIOL HAVING THESTRUCTURE
 2. A polymeric halogenated organophosphorus ester diol as setforth in claim 1 wherein R is hydrogen; and R'' is-CH2CH2-O-CH2CH2-O-CH2CH2-.
 3. A polymeric halogenated organophosphorusester diol as set forth in claim 2 wherein X is chlorine.
 4. A polymerichalogenated organophosphorus ester diol as set forth in claim 2 whereinX is bromine.
 5. A polymeric halogenated organophosphorus ester diol asset forth in claim 1 where R is hydrogen; and R'' is -CH2CH2-.
 6. Apolymeric halogenated organophosphorus ester diol as set forth in claim5 wherein X is bromine.
 7. A polymeric halogenated organophosphorusester diol as set forth in claim 1 wherein the
 8. A polymerichalogenated organophosphorus ester diol as set forth in claim 1 whereinR is hydrogen; and